Process for producing fluorinated polyvalent carbonyl compound

ABSTRACT

A fluorinated polyvalent carbonyl compound is produced by an economically advantageous method from inexpensive materials without requiring a complicated synthetic process step. Namely, the present invention comprises reacting a polyvalent alcohol having at least two kinds of alcohol skeletons selected among a primary alcohol, a secondary alcohol and a tertiary alcohol, with an acid halide to obtain a polyvalent ester compound, fluorinating it in a liquid phase to obtain a perfluorinated polyvalent ester compound, and cleaving the ester bonds derived from primary and secondary alcohols in the perfluoropolyvalent ester compound to obtain a fluorinated polyvalent carbonyl compound.

TECHNICAL FIELD

The present invention relates to a process for producing a fluorinatedpolyvalent carbonyl compound and a novel fluorinated polyvalent carbonylcompound.

BACKGROUND ART

A fluorinated carbonyl compound such as an acyl fluoride, aperfluoroketone or a perfluoroester, is a compound highly useful as e.g.an intermediate for preparation of various fluorinated compounds.Especially, a fluorinated polyvalent carbonyl compound having at leasttwo types of structures among the above-mentioned three types ofstructures, in one molecule, is very useful for the preparation of afluorinated compound having a plurality of functional groups.

A method for obtaining a perfluoroacyl fluoride and a perfluoroketone byfluorinating an acid halide and a ketone having respectivelycorresponding structures by an electrochemical fluorination method(hereinafter referred to as “an ECF method”), or a method for obtainingthem by pyrolyzing the ester bonds in perfluorinated alkyl estercompounds, has been known (see e.g. J. Am. Chem. Soc., 120, 7117(1998)).

However, in a case where a fluorinated polyvalent carbonyl compound isto be produced by the above prior art method, a polyvalent alkyl estercompound as a raw material for a perfluoropolyvalent alkyl estercompound to be pyrolyzed, is not readily available, and many complicatedsynthetic process steps will be required, whereby there have beenproblems such that the price of the perfluoropolyvalent alkyl estercompound is high, and available compounds are rather limited. Further,the prior art method has had a problem that the yield in the reactionfor the synthesis is low.

DISCLOSURE OF THE INVENTION

The present invention has been made in view of the above-mentionedproblems of the prior art and is intended to provide a process forproducing a fluorinated polyvalent carbonyl compound economicallyadvantageously from materials which are inexpensively available, withoutrequiring a complicated synthetic step.

The present inventors have conducted an extensive study to accomplishthe above object and as a result, have found it possible to obtain afluorinated polyvalent carbonyl compound without requiring a complicatedsynthetic step, by a process wherein a polyvalent alcohol having atleast two types of alcohol skeletons among a primary alcohol, asecondary alcohol and a tertiary alcohol, is used as a startingmaterial, and the polyvalent alcohol and an acid halide are reacted toobtain a polyvalent ester compound, which is fluorinated by a specificfluorination method, followed by cleaving the specific ester bonds.Further, it has been found that the above process is an economicallyadvantageous industrial production process, since the polyvalent alcoholis available inexpensively in various structures, and the presentinvention has been accomplished.

Namely, the present invention provides the following invention.

(a) A process for producing a compound of the following formula (5),which comprises reacting a compound of the following formula (1) with acompound of the following formula (2) to obtain a compound of thefollowing formula (3), then reacting the compound of the followingformula (3) with fluorine in a liquid phase to obtain a compound of thefollowing formula (4), and further cleaving the ester bonds derived fromthe primary and secondary alcohols in the compound of the formula (4):

wherein each of R¹, R², R³ and R⁴ which may be the same or different, isa monovalent organic group; Q^(H) is a (m+n+p)valent organic group;R^(1F), R^(2F), R^(3F), R^(4F) and Q^(F) are the same groups as R¹, R²,R³, R⁴ and Q^(H), respectively, or groups having R¹, R², R³, R⁴ andQ^(H) fluorinated, respectively; X is a halogen atom; otherwise, R² andR³, or R^(2F) and R^(3F), may, respectively, be connected to constitutea bivalent group; each of m, n and p is an integer of at least 0,provided that (m+n+p)≧2, and n and p are not 0 at the same time, andwhen m is 1, n is 1, and p is 0, or when m is 1, n is 0, and p is 1,Q^(H) may be a single bond, and when Q^(H) is a single bond, Q^(F) is asingle bond.

(b) The process wherein a compound of the following formula (6) isobtained, together with the compound of the formula (5), from thereaction product obtained by cleaving the ester bonds derived from theprimary and secondary alcohols in the compound of the formula (4):

wherein R^(4F) is as defined above.

(c) The process wherein the compound of the formula (2) has the samestructure as the compound of the formula (6), and at least a part of thecompound of the formula (6) obtained from the reaction product obtainedby cleaving the ester bonds in the compound of the formula (4) is usedas at least a part of the compound of the formula (2) to be reacted withthe compound of the formula (1), so that the compound of the formula (5)can be obtained continuously.

(d) A compound of the following formula (7), a compound of the followingformula (8), a compound of the following formula (9), a compound of thefollowing formula (1-1a) or a compound of the following formula (1-1b):

CH₃CH[OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃] CH₂OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃  (1-1a)CF₃CF[OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃] CF₂OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃  (1-1b)

BEST MODE FOR CARRYING OUT THE INVENTION

In this specification, a compound of the formula (1) will be representedby a compound (1). Compounds of other formulae will be representedsimilarly. In the present invention, firstly, a step (hereinafterreferred to as “an esterification step”) of reacting the compound (1)with the compound (2) to obtain a compound (3), is carried out.

The compound (1) to be used in the esterification step is a polyvalentalcohol having a structure in which m in number of —CH₂OH, n in numberof —CHR¹OH and p in number of —CR²R³OH being monovalent groups, arebonded to Q^(H). These monovalent groups are bonded to the same carbonatom or different carbon atoms in Q^(H), so that Q^(H) will be a(m+n+p)valent organic group. Otherwise, when m is 1, n is 1 and p is 0,Q^(H) may be a single bond. The compound (1) in such a case is thefollowing compound (1-1) having a group of —CH₂OH and a group of —CHR¹OHconnected. Otherwise, when m is 1, n is 0 and p is 1, Q^(H) may be asingle bond. The compound (1) in such a case is the following compound(1-2) having a group of —CH₂OH and a group of —CR²R³OH connected. Here,R¹, R² and R³ in the following formulae are as defined above.HOCH₂CHR¹OH  (1-1)HOCH₂CR²R³OH  (1-2)

In the above monovalent groups, each of R¹, R² and R³ which may be thesame or different, is a monovalent organic group. The monovalent organicgroup may, for example, be a monovalent hydrocarbon group, a monovalenthalogenated hydrocarbon group, a monovalent hetero atom-containinghydrocarbon group or a monovalent halogenated (hetero atom-containinghydrocarbon) group. In the present invention, each of R¹, R² and R³which may be the same or different, is preferably a monovalent saturatedorganic group having hydrogen atoms.

Here, the organic group, the hydrocarbon group, the halogenatedhydrocarbon group, the hetero atom-containing hydrocarbon group and thehalogenated (hetero atom-containing hydrocarbon) group are groups whichwill be defined hereinafter. In the present invention, the followingdefinitions will be used consistently even in such a case that the typesof compounds having these groups are different.

The organic group is a group containing at least one carbon atom, andthe hydrocarbon group is an organic group comprising carbon atoms andhydrogen atoms. Further, the halogenated hydrocarbon group means ahydrocarbon group wherein at least one hydrogen atom bonded to a carbonatom is substituted by a halogen atom. The hetero atom-containinghydrocarbon group is a hydrocarbon group containing a hetero atom (anoxygen atom, a nitrogen atom, a sulfur atom or the like) and/or a heteroatom group (such as —C—C(═O)—C— or —C—SO₂—C—). Further, the halogenated(hetero atom-containing hydrocarbon) group is a group having at leastone hydrogen atom bonded to a carbon atom in the above heteroatom-containing hydrocarbon group, substituted by a halogen atom.Further, in the present invention, a group wherein carbon-carbon bondsare solely single bonds, is identified by putting “saturated” before thename of the group. A “saturated” group may contain an unsaturated bond,so long as the carbon-carbon bonds in that group are single bonds.

Further, in the present invention, a group having at least one hydrogenatom bonded to a carbon atom substituted by a halogen atom, isidentified by putting “halogenated” before the name of the group.Especially, a group having substantially all hydrogen atoms bonded tocarbon atoms substituted by halogen atoms, is identified by putting“perhalogenated” before the name of the group. On the other hand, agroup having part of hydrogen atoms bonded to carbon atoms issubstituted by a halogen atom is identified by putting “partiallyhalogenated” before the name of the group. In these groups, when thehalogen atom is specified, for example, when the halogen atom is afluorine atom, “perfluoro”, “partially fluoro” or the like will be put.Further, halogen atoms in the “perhalogenated” group and the “partiallyhalogenated” group, may be of one type or two or more types.

Further, the “perhalogenated” group is preferably a group having allhydrogen atoms bonded to carbon atoms substituted by halogen atoms, buteven in a case where unsubstituted hydrogen atoms still remain, so longas the nature as a group is substantially equal to a “perhalogenated”group, such a group is included in the concept of the “perhalogenated”group in the present invention.

In a case where R¹, R² or R³ in the compound (1) is a monovalenthydrocarbon group, the carbon number is preferably from 1 to 20, morepreferably from 1 to 10. The monovalent hydrocarbon group may, forexample, be a monovalent aliphatic hydrocarbon group such as an alkylgroup, a monovalent alicyclic hydrocarbon group such as a cycloalkylgroup or a cycloalkylalkyl group, or a monovalent aromatic hydrocarbongroup such as a phenyl group, preferably a monovalent aliphatichydrocarbon group, more preferably an alkyl group. In the monovalentaliphatic hydrocarbon group, a single bond, a double bond or a triplebond may be present as a carbon-carbon bond. Further, the structure ofsuch a group may be a straight chain structure, a branched structure, acyclic structure or a structure partially having a cyclic structure.

The alkyl group is preferably a C₁₋₁₀ alkyl group, particularlypreferably a methyl group, an ethyl group or a propyl group. Thecycloalkyl group is preferably a cycloalkyl group of from 3- to6-membered ring or a group having at least one hydrogen atom of such acycloalkyl group substituted by an alkyl group. The cycloalkylalkylgroup is preferably a group having one hydrogen atom in a C₁₋₃ alkylgroup substituted by a cycloalkyl group, and as such a group, acyclohexylmethyl group may, for example, be mentioned.

In a case where R¹, R² or R³ in the compound (1) is a monovalenthalogenated hydrocarbon group, the type of the halogen atom is notparticularly limited, and a fluorine atom or a chlorine atom ispreferred. The monovalent halogenated hydrocarbon group may, forexample, be a fluoroalkyl group or a fluorochloroalkyl group. Further,the carbon number of the monovalent halogenated hydrocarbon group ispreferably from 1 to 20, more preferably from 1 to 10.

The monovalent halogenated hydrocarbon group may be a monovalentperhalogenated hydrocarbon group or a monovalent partially halogenatedhydrocarbon group, and its structure may be a straight chain structure,a branched structure or a structure partially having a cyclic structure.Further, such a group is preferably a saturated group.

The monovalent perhalogenated hydrocarbon group is preferably aperfluoroalkyl group or a perfluoro (partially chloroalkl) group whichis a group having substantially all hydrogen atoms in a partiallychlorinated alkyl group substituted by fluorine atoms.

In a case where R¹, R² or R³ in the compound (1) is a monovalent heteroatom-containing hydrocarbon group, the carbon number is preferably from1 to 20, more preferably from 1 to 10. The hetero atom in such a groupis preferably an etheric oxygen atom (—O—) or ═O. Further, the heteroatom may be in the form of a hetero atom group, and as such a heteroatom group, —C—C(═O)—C— or —C—SO₂—C— is preferred.

The hetero atom and the hetero atom group are preferably those whichundergo no change by pyrolysis and/or a fluorination reaction.Particularly preferred is an etheric oxygen atom. Further, as the heteroatom group, —C—C(═O)—C— or —C—SO₂—C— is preferred.

The monovalent hetero atom-containing hydrocarbon group is preferably anetheric oxygen atom-containing alkyl group, particularly preferably analkoxyalkyl group, from the viewpoint of availability, productionefficiency and usefulness of the product.

In a case where R¹, R² or R³ in the compound (1) is a monovalenthalogenated (hetero atom-containing hydrocarbon) group, it is preferablya group having at least one hydrogen atom bonded to a carbon atom in theabove monovalent hetero atom-containing hydrocarbon group substituted bya halogen atom. Here, the type of the halogen atom is not particularlylimited, and a fluorine atom or a chlorine atom is preferred.

The monovalent halogenated (hetero atom-containing hydrocarbon) groupmay, for example, be a fluoro (hetero atom-containing hydrocarbon) groupor a fluorochloro (hetero atom-containing hydrocarbon) group. Further,the carbon number of the monovalent halogenated (hetero atom-containinghydrocarbon) group is not particularly limited, and it is preferablyfrom 1 to 20, more preferably from 1 to 10.

The monovalent halogenated (hetero atom-containing hydrocarbon) groupmay be a monovalent perhalogenated (hetero atom-containing hydrocarbon)group or a monovalent partially halogenated (hetero atom-containinghydrocarbon) group. The perhalogenated group is preferably a monovalentperfluoro (hetero atom-containing hydrocarbon) group or a monovalentperfluoro (partially chlorinated (hetero atom-containing hydrocarbon))group. Further, the monovalent halogenated (hetero atom-containinghydrocarbon) group is preferably a saturated group, and its structuremay be a straight chain structure, a branched structure or a structurepartially having a cyclic structure.

The monovalent halogenated (hetero atom-containing saturatedhydrocarbon) group is preferably a fluoro(alkoxyalkyl) group or afluorochloro(alkoxyalkyl) group, and the monovalent perhalogenated(hetero atom-containing saturated hydrocarbon) group is preferably aperfluoro(alkoxyalkyl) group or a perfluoro (partially chlorinated(alkoxyalkyl)) group.

R² and R³ in the compound (1) to be used in the esterification step, maybe connected to form a bivalent group. Such a bivalent group may be abivalent organic group such as a bivalent hydrocarbon group, a bivalenthalogenated hydrocarbon group, a bivalent hetero atom-containinghydrocarbon group or a bivalent halogenated (hetero atom-containinghydrocarbon) group. Such a bivalent organic group is preferably a grouphaving one hydrogen atom or one halogen atom present in theabove-mentioned group such as a monovalent hydrocarbon group, amonovalent halogenated hydrocarbon group, a monovalent heteroatom-containing hydrocarbon group or a monovalent halogenated (heteroatom-containing hydrocarbon) group converted to a connecting bond. Thetype or combination of preferred halogen atoms, hetero atoms or heteroatom groups in such a bivalent group, is the same as described above.Further, the carbon number of the bivalent group is preferably from 2 to40, more preferably from 2 to 20, further preferably from 2 to 10.

The bivalent hydrocarbon group may, for example, be a straight chainalkylene group, a branched alkylene group or a cycloalkylene group, andthe bivalent halogenated hydrocarbon group may, for example, be a grouphaving some or all of hydrogen atoms bonded to carbon atoms in theabove-mentioned bivalent hydrocarbon group substituted by fluorine atomsand at least one type of halogen atoms other than fluorine atoms(preferably chlorine atoms).

Further, the bivalent hetero atom-containing hydrocarbon group may, forexample, be a group having from 1 to 6 (preferably from 1 to 3) ethericoxygen atoms inserted between carbon-carbon bonds of the above-mentionedbivalent hydrocarbon group.

Further, the bivalent halogenated (hetero atom-containing hydrocarbon)group may, for example, be a group having some or all of hydrogen atomsbonded to carbon atoms in a bivalent hetero atom-containing hydrocarbongroup substituted by fluorine atoms or at least one type of halogenatoms other than fluorine atoms (preferably chlorine atoms). As such agroup, preferred is a fluorochloro(etheric oxygen atom-containingalkylene) group, a perfluoro (etheric oxygen atom-containing alkylene)group or a perfluoro (partially chlorinated (etheric oxygenatom-containing alkylene)) group.

Q^(H) in the compound (1) is a (m+n+p) valent organic group, and such anorganic group is preferably a hydrocarbon group, a halogenatedhydrocarbon group, a hetero atom-containing hydrocarbon group or ahalogenated (hetero atom-containing hydrocarbon) group. Further, Q^(H)is preferably a (m+n+p) valent saturated organic group having hydrogenatoms. Such a saturated organic group is preferably a saturatedhydrocarbon group or a hetero atom-containing saturated hydrocarbongroup.

The hetero atom in the (m+n+p) valent hetero atom-containing saturatedhydrocarbon group, is the same as described above, and it is preferablyone which undergoes no change by pyrolysis and/or a fluorinationreaction, and an etheric oxygen atom is preferred. Further, it may be agroup which contains a hetero atom group such as —C—C(═O)—C— or—C—SO₂—C—.

The structure of Q^(H) may be a straight chain structure, a branchedstructure, a cyclic structure or a structure partially having a cyclicstructure. Further, the carbon number of Q^(H) is preferably from 1 to20, particularly preferably from 1 to 10.

Further, in a case where m is 1, n is 1 and p is 0, or in a case where mis 1, n is 0 and p is 1, Q^(H) may be a bivalent organic group or asingle bond.

The compound (1) to be used in the esterification step, is a polyvalentalcohol having a structure in which m in number of —CH₂OH group, n innumber of —CHR¹OH group and p in number of —CR²R³OH group, are bonded toQ^(H). Or, the compound (1) is, like the above compound (1-1) or theabove compound (1-2), a bihydric alcohol wherein one of the terminals isa primary hydroxyl group, and the other terminal is a secondary hydroxylgroup or a tertiary hydroxyl group.

The compound (3) formed by the reaction of the compound (1) with thecompound (2), is then reacted with fluorine in a liquid phase. Toimprove the solubility of the compound (3) in the liquid phase for thispurpose, the compound preferably has a structure containing halogenatoms (preferably fluorine atoms). Accordingly, at least one of R¹, R²,R³, R⁴ and Q^(H) in the compound (3) is preferably a group containinghalogen atoms (preferably fluorine atoms). Further, in order toefficiently obtain the fluorinated polyvalent carbonyl compound of thepresent invention at a low cost, it is preferred to employ as thecompound (1) a compound containing no halogen atoms such as fluorineatoms and to employ as the compound (2) one containing halogen atomssuch as fluorine atoms.

Accordingly, R¹, R² or R³ in the compound (1) is particularly preferablya monovalent hydrocarbon group such as an alkyl group or a monovalenthetero atom-containing hydrocarbon group such as an alkoxy group or analkoxyalkyl group, among the above-mentioned monovalent organic groups,and Q^(H) is particularly preferably a (m+n+p)valent saturatedhydrocarbon group. R¹, R² or R³ is most preferably an alkyl group.Further, in the compound (1), it is preferred that m is an integer of atleast 1, n is an integer of at least 0, and p is an integer of atleast 1. Further, m in the compound (1) is more preferably an integer offrom 1 to 10, further preferably 1 or 2. n is more preferably an integerof from 0 to 10, particularly preferably an integer of from 0 to 2. p ismore preferably an integer of from 0 to 10, particularly preferably aninteger of from 0 to 2.

Further, in the compound (1), it is also preferred that m is an integerof at least 1, n is an integer of at least 1, and p is an integer of atleast 0.

Further, in a case where m is 1, n is 1 and p is 0, or in a case where mis 1, n is 0 and p is 1, each of R¹, R² and R³ in a case where Q^(H) isa single bond, is preferably an alkyl group, particularly preferably amethyl group.

In the esterification step, the compound (1) and the compound (2) arereacted.

In the compound (2), R⁴ is a monovalent organic group, and themonovalent organic group may, for example, be a monovalent hydrocarbongroup, a monovalent halogenated hydrocarbon group, a monovalent heteroatom-containing hydrocarbon group or a monovalent halogenated (heteroatom-containing hydrocarbon) group. The definitions and specificexamples for the monovalent hydrocarbon group, the monovalenthalogenated hydrocarbon group, the monovalent hetero atom-containinghydrocarbon group and the monovalent halogenated (hetero atom-containinghydrocarbon) group, are as described above.

As mentioned above, from the viewpoint of the economical efficiency andavailability of starting materials, R⁴ in the compound (2) is preferablya monovalent organic group containing halogen atoms (preferably fluorineatoms). R⁴ is more preferably a monovalent perhalogenated organic group,particularly preferably a monovalent perfluorinated organic group.Namely, R⁴ is preferably a monovalent perfluorinated saturatedhydrocarbon group, a monovalent perfluoro (partially chlorinatedsaturated hydrocarbon) group, a monovalent perfluoro (heteroatom-containing saturated hydrocarbon) group or a monovalent perfluoro(partially chlorinated (hetero atom-containing saturated hydrocarbon))group.

In the compound (2), X is a halogen atom. The halogen atom may be afluorine atom, a chlorine atom, a bromine atom or an iodine atom. Amongthem, a fluorine atom, a chlorine atom or a bromine atom is preferred,and a fluorine atom or a chlorine atom is more preferred. A fluorineatom is particularly preferred.

The reaction of the compound (1) and the compound (2) can be carried outunder the conditions for a known esterification reaction. The reactionmay be carried out in the presence of a solvent (hereinafter referred toas “solvent 1”), but it is preferred to carry out the reaction in theabsence of solvent 1, from the viewpoint of the volume efficiency. In acase where solvent 1 is employed, dichloromethane, chloroform,triethylamine or a mixed solvent of triethylamine and tetrahydrofuran,is preferred. The amount of solvent 1 to be used is preferably from 50to 500 mass %, based on the total amount of the compound (1) and thecompound (2).

By the reaction of the compound (1) and the compound (2), an acidrepresented by HX will be generated. In a case where a compound whereinX is a fluorine atom, is employed as the compound (2), HF will begenerated, and as a HF scavenger, an alkali metal fluoride (preferablyNaF or KF) or a trialkylamine may be permitted to be present in thereaction system. In a case where the compound (1) or the compound (2) isa compound unstable against an acid, it is preferred to use a scavengerfor HF. Further, in a case where no HF scavenger is used, it ispreferred to discharge HF out of the reaction system, as accompanied bya nitrogen stream. In a case where an alkali metal fluoride is employed,its amount is preferably from 1 to 10 mols per mol of the compound (2).

The temperature for the reaction of the compound (1) and the compound(2) is preferably at least −50° C. and preferably at most the boilingpoint of the solvent and at most +100° C. Further, the reaction time forthe reaction may suitably be changed depending upon the supply rates ofthe starting materials and the amounts of the compounds to be used forthe reaction. The pressure for the reaction (gauge pressure, the sameapplies hereinafter) is preferably from atmospheric pressure to 2 MPa.

The compound (3) to be formed by the reaction of the compound (1) andthe compound (2) is preferably a compound which is readily soluble in aliquid phase when the after-mentioned fluorination is carried out in theliquid phase and which has a molecular weight sufficient to prevent thedecomposition reaction. Namely, the molecular weight of the compound (3)is preferably from 200 to 1,000. If the molecular weight is less than200, the compound (3) tends to be vaporized, whereby during thefluorination reaction in a liquid phase, a decomposition reaction in agas phase is likely to take place. On the other hand, if the molecularweight exceeds 1,000, purification of the compound (3) tends to bedifficult.

Further, in a case where the compound (3) is a fluorinated compound, thefluorine content in the compound (3) (the proportion of fluorine atomsin the molecule) is preferably suitably changed depending upon the typeof the after-mentioned liquid phase. Usually, the fluorine content ispreferably at least 30 mass %, more preferably from 30 to 86 mass %,further preferably from 30 to 76 mass %.

The crude product containing the compound (3) formed by the reaction ofthe compound (1) and the compound (2), may be purified depending uponthe particular purpose or may be used for e.g. the subsequent reactionas it is. It is advisable to purify the crude product so that thefluorination reaction in the next step can be proceeded smoothly.

As the method for purifying the crude product, a method of distillingthe crude product as it is, a method of treating the crude product witha dilute alkali aqueous solution, followed by liquid separation, amethod of extracting the crude product with a suitable organic solvent,followed by distillation, or silica gel column chromatography, may, forexample, be mentioned.

Then, a step (hereinafter referred to as a “fluorination step”) ofreacting the above compound (3) with fluorine in a liquid phase toobtain a compound (4), is carried out. The fluorination reaction in thefluorination step is carried out in a liquid phase from the viewpoint ofthe operation efficiency for the reaction and the yield. Such afluorination reaction can be theoretically carried out even by an ECFmethod, a cobalt fluorination method or a method of reacting it withfluorine in a gas phase, but fluorination in a liquid phase is aremarkably advantageous method from the viewpoint of e.g. the yield andthe operation efficiency of the reaction.

The fluorination reaction can be carried out by a method wherein thecompound (3) and fluorine (F₂) are reacted in the presence of a solvent(hereinafter referred to as “solvent 2”) to obtain a compound (4). Sucha method is a method so-called liquid phase fluorination. As thefluorine, fluorine gas may be used as it is, or fluorine gas dilutedwith an inert gas, may be employed. As such an inert gas, nitrogen gasor helium gas is preferred, and from the economical reason, nitrogen gasis particularly preferred. The amount of fluorine in the inert gas suchas nitrogen gas, is not particularly limited, and it is preferably atleast 10 vol % from the viewpoint of the efficiency, particularlypreferably at least 20 vol %.

Solvent 2 is preferably a solvent which contains no C—H bond and whichessentially contains a C—F bond, and it is further preferably aperfluoroalkane or an organic solvent obtained by perfluorinating aknown organic solvent containing in its structure at least one type ofatom selected from the group consisting of a chlorine atom, a nitrogenatom and an oxygen atom. Further, as solvent 2, it is preferred toemploy a solvent which dissolves the compound (3) with a highsolubility, specifically a solvent which is capable of dissolving atleast 1 mass % of the compound (3), particularly preferably a solventcapable of dissolving at least 5 mass % thereof.

As an example of solvent 2, a compound of the following formula (6), aperfluoroalkane (such as FC-72, tradename), a perfluoroether (such asFC-75 or FC-77), a perfluoropolyether (such as Krytox, Fonbrine, Gardenor Demnum, tradename), a chlorofluorocarbon (Flonrube, tradename), achlorofluoropolyether, a perfluoroalkylamine (such as aperfluorotrialkylamine), or an inert fluid (Florinate, tradename) may,for example, be mentioned. Among them, a perfluorotrialkylamine or acompound (6) is preferred. Especially when the compound (6) is employed,post treatment after the reaction can be facilitated, such beingadvantageous. The amount of solvent 2 is preferably at least 5 times bymass, particularly preferably from 10 to 100 times by mass, based on thecompound (3).

The reaction system for the fluorination reaction may be a batch systemor a continuous system. Further, the fluorination reaction is preferablycarried out by the following fluorination method 1 or 2, and from theviewpoint of the yield and selectivity in the reaction, it is preferredto carry out the reaction by fluorination method 2. Further, as thefluorine gas, one diluted with an inert gas such as nitrogen gas may beused either in a case where the reaction is carried out by a batchsystem or in a case where the reaction is carried out by a continuoussystem.

Fluorination Method 1

A method which comprises charging the compound (3) and solvent 2 into areactor, initiating stirring, controlling the temperature and pressureto the prescribed reaction temperature and reaction pressure, and thencontinuously supplying fluorine gas, or fluorine gas and solvent 2, tocarry out the reaction.

Fluorination Method 2

A method which comprises charging solvent 2 into a reactor, initiatingstirring, controlling the temperature and pressure to the prescribedreaction temperature and reaction pressure, and then continuously andsimultaneously supplying the compound (3) and fluorine gas at aprescribed molar ratio.

When the compound (3) is supplied in the continuous system 2, it ispreferred to supply the compound (3) diluted with solvent 2, in order toimprove the selectivity and to suppress the amount of by-products.Further, when the compound (3) is diluted with the solvent in thecontinuous system 2, the amount of solvent 2 to the compound (3) isadjusted to be preferably at least 5 times by mass, particularlypreferably at least 10 times by mass.

The amount of fluorine to be used for the fluorination reaction ispreferably adjusted to be such an amount that the amount of fluorinewill be always in excess equivalent to the hydrogen atoms to befluorinated in either case of carrying out the reaction by a batchsystem or by a continuous system, and it is particularly preferablyadjusted to be at least 1.5 times by equivalent (i.e. at least 1.5 mols)to the hydrogen atoms, from the viewpoint of the selectivity. The amountof fluorine is preferably maintained to be always in excess equivalentfrom the initiation of the reaction to the end of the reaction.

The reaction temperature for the fluorination reaction is usuallypreferably at least −60° C. and at most the boiling point of thecompound (3), and from the viewpoint of the yield, selectivity andindustrial applicability of the reaction, it is particularly preferablyfrom −50° C. to +100° C., especially preferably from −20° C. to +50° C.The reaction pressure for the fluorination reaction is not particularlylimited, and it is particularly preferably from atmospheric pressure to2 MPa from the viewpoint of the yield, selectivity and industrialapplicability of the reaction.

Further, in order to have the fluorination reaction proceededefficiently, it is preferred to add a C—H bond-containing compound tothe reaction system or to carry out ultraviolet ray irradiation, at alater stage of the reaction. For example, it is preferred that at alater stage of the fluorination reaction, a C—H bond-containing compoundis added to the reaction system, or ultraviolet ray irradiation iscarried out. By the use of a C—H bond-containing compound, the compound(3) present in the reaction system can efficiently be fluorinated,whereby the conversion can remarkably be improved.

The C—H bond-containing compound is an organic compound other than thecompound (3), particularly preferably an aromatic hydrocarbon,especially preferably benzene, toluene or the like. The amount of theC—H bond-containing compound to be added, is preferably from 0.1 to 10mol %, particularly preferably from 0.1 to 5 mol %, based on hydrogenatoms in the compound (3).

The C—H bond-containing compound is preferably added in a state wherefluorine gas is present in the reaction system. Further, when a C—Hbond-containing compound is added, the reaction system is preferablypressurized. The pressure for pressurizing is preferably from 0.01 to 5MPa.

By the fluorination step, the compound (3) is fluorinated to form acompound (4). In the compound (4), R^(1F) corresponds to R¹, R^(2F)corresponds to R², R^(3F) corresponds to R³, R^(4F) corresponds to R⁴,and Q^(F) correspond to Q^(H). In a case where R¹, R², R³, R⁴ and Q^(H)are groups to be fluorinated, respectively, and have been actuallyfluorinated, R^(1F), R^(2F), R^(3F), R^(4F) and Q^(F) are groups havingR¹, R², R³, R⁴ and Q^(H) fluorinated, respectively. For example, in acase where R¹, R², R³, R⁴ and Q^(H) are groups containing hydrogenatoms, if they are fluorinated, R^(1F), R^(2F), R^(3F), R^(4F) and Q^(F)are groups having at least one hydrogen atom in R¹, R², R³, R⁴ and Q^(H)substituted by a fluorine atom. Further, in a case where a —CH═CH—portion or a —C≡C— portion is present in R¹, R², R³, R⁴ or Q^(H),fluorine atoms may be added to such a portion by the fluorination stepto form —CF₂CF₂—. On the other hand, in a case where R¹, R², R³, R⁴ andQ^(H) are groups not fluorinated, or even if they are groups which canbe fluorinated, if they are not fluorinated, R^(1F), R^(2F), R^(3F),R^(4F) and Q^(F) are the same groups as R¹, R², R³, R⁴ and Q^(H),respectively. In the fluorination reaction in the liquid phase in thepresent invention, hydrogen atoms bonded to carbon atoms in R¹, R², R³,R⁴ and Q^(H), will be substituted by fluorine atoms, but chlorine atoms,bromine atoms or iodine atoms bonded to carbon atoms will not besubstituted by fluorine atoms. Further, in a case where Q^(H) is asingle bond, Q^(F) will be a single bond.

In the present invention, it is preferred that in the fluorinationreaction, the compound (3) is perfluorinated. Further, R¹, R² and R³ maybe the same or different and are preferably a monovalent saturatedorganic group having hydrogen atoms. In such a case, R^(1F), R^(2F) andR^(3F) are preferably a monovalent perfluorinated saturated organicgroup having all hydrogen atoms in said saturated organic groupsubstituted by fluorine atoms. In the present invention, it is alsopreferred that Q^(H) is a (m+n+p)valent saturated organic group havinghydrogen atoms, and in such a case, Q^(F) is preferably a (m+n+p)valentperfluorinated saturated organic group having all hydrogen atoms inQ^(H) substituted by fluorine atoms.

The compound (3) wherein R¹, R², R³, R⁴ and Q^(H) are a saturatedhydrocarbon group, a halogenated saturated hydrocarbon group, a heteroatom-containing saturated hydrocarbon group or a halogenated (heteroatom-containing saturated hydrocarbon) group, is preferably such thatall hydrogen atoms in such a group are substituted by fluorine atoms.

Accordingly, each of R^(1F), R^(2F), R^(3F) and R^(4F) is preferably amonovalent perfluoro saturated hydrocarbon group, a monovalent perfluoro(partially halogenated saturated hydrocarbon) group, a monovalentperfluoro (hetero atom-containing saturated hydrocarbon) group or amonovalent perfluoro (halogenated (hetero atom-containing saturatedhydrocarbon)) group, and Q^(F) is preferably a (m+n+p)valentperfluorinated saturated hydrocarbon group, a (m+n+p)valent perfluoro(partially halogenated saturated hydrocarbon) group, a (m+n+p)valentperfluoro (hetero atom-containing saturated hydrocarbon) group or a(m+n+p)valent perfluoro (partially halogenated (hetero atom-containingsaturated hydrocarbon)) group.

In the compound (4), R^(2F) and R^(3F) may be connected to form abivalent group. In the present invention, R² and R³ which are notconnected, will not be connected in the process of the abovefluorination. Accordingly, a bivalent group having R^(2F) and R^(3F)connected to each other, is a group corresponding to a bivalent grouphaving R² and R³ connected to each other. Namely, a bivalent grouphaving R^(2F) and R^(3F) connected to each other, is a group obtained byfluorination of a bivalent group having R² and R³ connected to eachother. Here, in a case where a bivalent group having R² and R³ connectedto each other, is a non-fluorinated group, the bivalent group havingR^(2F) and R^(3F) connected to each other will be the same as thebivalent group having R² and R³ connected to each other.

Such a bivalent group having R^(2F) and R^(3F) connected to each other,may, for example, be a bivalent perfluorinated saturated hydrocarbongroup, a bivalent perfluoro (partially halogenated saturatedhydrocarbon) group, a bivalent perfluoro (hetero atom-containingsaturated hydrocarbon) group or a bivalent perfluoro (partiallyhalogenated (hetero atom-containing saturated hydrocarbon)) group. Amongthem, a perfluoroalkylene group or a perfluoro(alkyleneoxyalkylene)group is preferred.

In a case where a reaction to substitute hydrogen atoms by fluorineatoms takes place in the reaction for fluorinating the compound (3) in aliquid phase, HF will be formed as a by-product. To remove theby-product HF, it is preferred to permit a HF scavenger to be present inthe reaction system or to let the outlet gas contact with a HF scavengerat the gas outlet of the reactor. As such a HF scavenger, the same oneas described above may be employed, and NaF is preferred.

The amount of the HF scavenger to be permitted to be present in thereaction system, is preferably from 1 to 20 times by mol, particularlypreferably from 1 to 5 times by mol, based on the total amount ofhydrogen atoms present in the compound (3). In a case where the HFscavenger is placed at the gas outlet of the reactor, it is preferred toarrange (a) a cooler (which is preferably maintained at from 10° C. toroom temperature, particularly preferably at about 20° C.) (b) a layerpacked with NaF pellets and (c) a cooler (which is preferably maintainedat from −78° C. to +10° C., more preferably from −30° C. to 0° C.) inseries in the order of (a)-(b)-(c). Further, a liquid returning line maybe installed to return the condensed liquid from the cooler (c) to thereactor.

The crude product containing the compound (4) obtained in thefluorination step may be used as it is in the subsequent step or may bepurified to be highly pure. The purification method may, for example, bea method of distilling the crude product as it is under normal pressureor reduced pressure.

Then, a step (hereinafter referred to as a “cleavage step”) of cleavingthe ester bonds derived from the primary and secondary alcohols in thecompound (4) to obtain a compound (5), is carried out.

The cleavage step is preferably carried out by a cleavage reaction whichis carried out by a pyrolytic reaction or in the presence of anucleophilic agent or an electrophilic agent.

The pyrolytic reaction can be carried out by heating the compound (4).As the reaction system for the pyrolytic reaction, it is preferred toselect it depending upon the boiling point and the stability of thecompound (4). For example, in a case where a readily vaporizablecompound (4) is subjected to pyrolysis, it is possible to employ a gasphase pyrolytic method wherein the decomposition is carried outcontinuously in a gas phase, and an outlet gas containing the obtainedcompound (5) is condensed and recovered.

The reaction temperature for the gas phase pyrolysis is preferably from50 to 350° C., more preferably from 50 to 300° C., particularlypreferably from 150 to 250° C. Further, in the reaction, an inert gaswhich will not be involved directly in the reaction, may be present inthe reaction system. As such an inert gas, nitrogen, or carbon dioxidemay, for example, be mentioned. The inert gas is preferably added in anamount of from 0.01 to 50 vol %, based on the compound (4). If theamount of the inert gas added, is large, the amount of the product to berecovered may decrease.

On the other hand, in a case where the compound (4) is a compound whichis hardly vaporized, it is preferred to adopt a liquid phase pyrolyticmethod wherein it is heated in the form of a liquid in the reactor. Thereaction pressure in such a case is not particularly limited. In a usualcase, the product containing the compound (5) has a low boiling point.Accordingly, it is preferably obtained by a method of a reactiondistillation system wherein the product is vaporized and continuouslywithdrawn. Further, it may be a method wherein the product is withdrawnall at once from the reactor after completion of the heating. Thereaction temperature for such a liquid phase pyrolysis is preferablyfrom 50 to 300° C., particularly preferably 100 to 250° C.

The pyrolysis by a liquid phase pyrolytic method may be carried out inthe absence or presence of a solvent (hereinafter referred to as“solvent 3”). Solvent 3 is not particularly limited so long as it doesnot react with the compound (4) and has a compatibility with thecompound (4) and it is not reactive with the resulting compound (5).Further, as solvent 3, it is preferred to select one which can easily beseparated at the time of purification of the compound (5). As a specificexample of solvent 3, an inert solvent such as a perfluorotrialkylamineor a perfluoronaphthalene, or among chlorofluorocarbons, achlorotrifluoroethylene oligomer (such as Flonrube, tradename) which hasa high boiling point among chlorofluorocarbons, is preferred. Further,the amount of solvent 3 is preferably from 10 to 1,000 mass %, based onthe compound (4).

Further, in a case where the compound (4) is reacted with a nucleophilicagent or an electrophilic agent for cleavage, such a reaction may becarried out in the absence or presence of a solvent (hereinafterreferred to as “solvent 4”). As solvent 4, the same one as solvent 3 ispreferred. As the nucleophilic agent, F⁻ is preferred. Particularlypreferred is F⁻ derived from an alkali metal fluoride. The alkali metalfluoride is preferably NaF, NaHF₂, KF or CsF. Among them, NaF isparticularly preferred from the viewpoint of economical efficiency.

In a case where a nucleophilic agent (such as F⁻) is employed, thenucleophilic agent employed at the initial stage of the reaction may bein a catalytic amount or may be in an excess amount. Namely, the amountof the nucleophilic agent such as F⁻ is preferably from 1 to 500 mol %,more preferably from 1 to 100 mol %, particularly preferably from 5 to50 mol %, based on the compound (4). The reaction temperature ispreferably from −30° C. to the boiling point of the solvent or thecompound (4), particularly preferably from −20° C. to 250° C. Thismethod is also preferably carried out by a reaction distillation system.

By the cleavage reaction of compound (4), the ester bond derived fromthe primary alcohol is cleaved to a —COF residue, and the ester bondderived from the secondary alcohol is cleaved to a —COR^(1F) residue,whereby the ester bond derived from the tertiary alcohol will notchange. Accordingly, by the cleavage reaction of the compound (4), thecompound (5) will be formed.

In the process for producing a fluorinated polyvalent carbonyl compoundof the present invention, it is possible to obtain the followingcompound (6) at the same time as the compound (5) by the cleavage of theester bonds derived from the first and second alcohols in the compound(4). The reaction scheme from the compound (1) to the compound (6) inthis case can be represented by the following chemical formulae,provided that the symbols in the following formulae have the samemeanings as described above.

In the present invention, R⁴ in the compound (2) and R^(4F) in thecompound (6) are preferably of the same structure, particularlypreferably of the same monovalent perfluorinated saturated organicgroup. Further, in a case where the compound (2) and the compound (6)are of the same structure, it is possible to produce the compound (5)continuously by using at least a part of the compound (6) obtained fromthe reaction product obtained by the cleavage of the ester bonds of thecompound (4), as at least a part of the compound (2) to be reacted withthe compound (1). The reaction scheme of the compound (1), the compound(2) (i.e. the compound (6)), and the compounds (3) to (6) in such a casecan be represented by the following chemical formulae.

The compound (2) being of the same structure as the compound (6) meansthat R⁴ in the compound (2) is R^(4F) in the compound (6), and X in thecompound (2) is a fluorine atom. In such a case, the compound (2) willbe the same as the compound (6), whereby R⁴ is R^(4F), and R⁴ ispreferably a monovalent perfluoroalkyl group, a monovalent perfluoro(partially chlorinated) alkyl group, a monovalent perfluoro (ethericoxygen atom-containing alkyl) group or a monovalent perfluoro (partiallychlorinated (etheric oxygen atom-containing alkyl)) group. As describedin the foregoing, according to the process of the present invention, itis made possible to produce various fluorinated polyvalent carbonylcompounds (compounds (5)) in high yield by a short process by means ofthe compound (1) and the compound (2) which are materials available atlow costs. Further, it is possible to obtain an acid fluoride compound(compound (6)) together with the fluorinated polyhydric carbonylcompound (compounds (5)).

Further, by employing the process of the present invention, it ispossible to readily synthesize a fluorinated polyvalent carbonylcompound having a complex structure or a fluorinated polyvalent carbonylcompound having a low molecular weight, which used to be difficult toobtain by conventional methods. Further, the process of the presentinvention is not limited to the compounds disclosed in Examples, and isa process excellent in common applicability which can be applied tovarious compounds, whereby a fluorinated polyvalent carbonyl grouphaving a desired skeleton can freely be prepared. Further, the processof the present invention can be made a continuous process, and assolvent 2 to be used in the case of reacting the compound (3) withfluorine in a liquid phase, the compound (6) as a reaction product canbe reused. Accordingly, the amounts of the starting materials to be usedor the amount of wastes can be reduced, and the fluorinated polyvalentcarbonyl compound can be prepared economically very efficiently.

One embodiment of the process of the present invention will be shown inthe following reaction scheme. In this reaction scheme, the followingcompound (10) and the following compound (11) are reacted to obtain thefollowing compound (7), then, the compound (7) is reacted with fluorinein a liquid phase to obtain the following compound (8), and further, theester bond derived from the primary alcohol in the compound (8) iscleaved to obtain the following compound (9) and the following compound(12). X in the compound (11) represents a halogen atom, and when X is afluorine atom, the chemical structure will be the same as the compound(12), whereby the compound (9) can be continuously obtained by employingat least a part of the compound (12) as at least a part of the compound(11).

The compound (7), the compound (8) and the compound (9) in the abovereaction scheme are novel chemical substances. The compound (9) as oneof fluorinated polyvalent carbonyl compounds, is useful as anintermediate for the preparation of various fluorinated compounds, andthe compound (7) and the compound (8) are useful as intermediates forthe preparation of the compound (9). For example, the compound (9) maybe reacted with hexafluoropropylene oxide, followed by pyrolysis toobtain CF₂═CFO(CF₂)₂C(CF₃)₂OCOCF₂CF₃, which may further be hydrolyzed toobtain CF₂═CFO(CF₂)₂C(CF₃)₂OH. CF₂═CFO(CF₂)₂C(CF₃)₂OH has a hydroxylgroup and a polymerizable unsaturated double bond in its molecule and isvery useful as a starting material for a functional polymer.

Further, perfluoropyruvic acid fluoride (CF₃COCOF) which can be producedby the process of the present invention via the compound (1-1a) and thecompound (1-1b), is a compound useful as a base material forpharmaceuticals.

EXAMPLES

Now, the present invention will be described in detail with reference toExamples, but the present invention is by no means thereby restricted.In the following, gas chromatography will be referred to as GC, and gaschromatographic mass analysis will be referred to as GC-MS. Further, thepurity obtained from the peak area ratio of GC will be referred to as GCpurity, and the yield will be referred to as GC yield. The yieldobtained from the peak area ratio of the NMR spectrum will be referredto as NMR yield. Further, tetramethylsilane will be referred to as TMS,CCl₂FCClF₂ will be referred to as R-113, and dichloropentafluoropropanemanufactured by Asahi Glass Company, Limited will be referred to asAK-225. Further, the NMR spectrum data was shown as an apparent chemicalshift range. The standard value for the standard substance CDCl₃ in¹³C-NMR was 76.9 ppm. In the quantative analysis by ¹⁹F-NMR, C₆F₆ wasemployed as an internal standard.

Example 1 Example 1-1 Example for Esterification Step

CH₂Cl₂ (509 g), pyridine (177 g) and HOC(CH₃)₂CH₂CH₂OH (20 g) were putinto a flask and stirred while bubbling nitrogen gas. CF₃CF₂COF (72 g)was fed over a period of two hours while maintaining the internaltemperature at a level of from −5° C. to +4° C. After completion of thefeeding, the reaction crude liquid was dropwise added to a 5 mass %hydrochloric acid aqueous solution (1,400 g) while maintaining theinternal temperature at a level of at most 2° C. After liquidseparation, washing with a hydrochloric acid aqueous solution wasfurther carried out, followed by liquid separation to obtain an organiclayer (500 g). Further, the organic layer was washed with a 5 mass %sodium hydrogencarbonate solution (470 g), and subjected to liquidseparation, whereupon the organic layer was washed with water (520 ml)and dried over magnesium sulfate, followed by filtration to obtain acrude liquid (450 g). The crude liquid was concentrated by an evaporatorand then distilled under reduced pressure to obtain a fraction (47 g) of61° C./0.3 kPa. This fraction was purified by silica gel columnchromatography (developing solvent: AK-225) to obtain a purified product(43.1 g). The GC purity was 98%. From the NMR spectrum, it was confirmedthat the following compound (7) was the main component. Further, the NMRspectrum data were as shown below.

¹H-NMR (399.0 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.64 (s, 6H),2.31 (t, J=6.6 Hz, 2H), 4.51 (t, J=6.6 Hz, 2H).

¹⁹F-NMR (376.0 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −83.8(6F), −122.5 (4F).

Example 1-2 Example for Fluorination Step

Into a 200 mL nickel autoclave, R-113 (156 g) was added, stirred andmaintained at 25° C. At the gas outlet of the autoclave, a coolermaintained at −10° C. and a pressure controlling bulb were installed inseries. Nitrogen gas was supplied for one hour. Then, fluorine gasdiluted to 20% by nitrogen gas was supplied at a flow rate of 5.77 L/hrfor one hour, and the internal pressure of the reactor was adjusted to0.15 MPa. Then, diluted fluorine gas was supplied at the same flow rate,and while adjusting the internal pressure of the reactor to 0.15 MPa, asolution obtained by dissolving the compound (7) (4.01 g) obtained inthe esterification step, in R-113 (80 g), was injected over a period of5.8 hours.

Then, diluted fluorine gas was supplied at the same flow rate, and whileadjusting the internal pressure of the reactor to 0.15 MPa, abenzene/R-113 solution having a concentration of 0.01 g/mL was injectedin an amount of 6 ml while raising the temperature from 25° C. to 40°C., whereupon stirring was continued for 0.2 hour. Then, dilutedfluorine gas was supplied at the same flow rate, and while maintainingthe internal temperature of the reactor at 40° C. and the internalpressure of the reactor at 0.15 MPa, the above-mentioned benzenesolution (3 ml) was injected, whereupon stirring was continued for 0.2hour. Further, the same operation was repeated five times. The totalamount of benzene injected was 0.245 g, and the total amount of R-113injected was 24 ml. Further, diluted fluorine gas was supplied for onehour, and nitrogen gas was supplied for 1.5 hours. The yield by ¹⁹F-NMRof the obtained compound was 49%. Further, from the results of ¹⁹F-NMR,the obtained compound was found to be the following compound (8). TheNMR spectrum data were as follows.

¹⁹F-NMR (376.0 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −67.3(6F), −67.5 (2F), −83.1 (3F), −83.2 (3F), −116.1 (2F), −121.1 (2F),−122.2 (2F).

Example 1-3 Example for Step for Cleavage of Ester Bonds

The compound (8) (0.5 g) obtained in the fluorination step was chargedinto a flask together with NaF powder (0.02 g) and heated at 100° C. for3.5 hours and at 120° C. for 2.5 hours, in an oil bath while vigorouslystirring. At the upper portion of the flask, a reflux condenser havingthe temperature adjusted at 20° C. and a gas sampling bag were disposedin series. After cooling, a liquid sample (0.4 g) and a gas sample (0.1g) were recovered. As a result of the analysis by GC-MS, in the liquidsample, the following compound (9) was confirmed to be the main product,and in the gas sample, CF₃CF₂COF was confirmed to be the main product.The yield of the compound was obtained by NMR and found to be 44.0%.Further, the NMR spectrum data were as follows.

¹⁹F-NMR (376.0 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): 23.4 (1F),−68.2 (6F), −83.1 (3F), −108.5 (2F), −121.3 (2F).

Example 2 Example 2-1 Example for Production ofCH₃CH[OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃]CH₂OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃by Esterification Reaction

CH₃CH(OH)CH₂OH (10.0 g) was put into a flask and stirred while bubblingnitrogen gas. FCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃ (137.6 g) was dropwiseadded over a period of 40 minutes, while maintaining the internaltemperature at from 28 to 30° C. After completion of dropwise addition,stirring was carried out for 7 hours while maintaining the internaltemperature at 30° C., and 150 ml of a saturated sodiumhydrogencarbonate aqueous solution was added at an internal temperatureof at most 15° C.

The obtained crude liquid was subjected to liquid separation to obtain afluorocarbon layer. Further, the fluorocarbon layer was washed twicewith 50 ml of water, dried over magnesium sulfate and then filtered toobtain a crude liquid. The crude liquid was purified by silica gelcolumn chromatography (developing solvent: AK-225) to obtain the aboveidentified compound (73.1 g), the formed product. The purity by GC was99%. The NMR spectrum data were as follows.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: CHCl₃) δ (ppm): 1.39 to1.45 (m, 3H), 4.28 to 4.70 (m, 2H), 5.35 to 5.47 (m, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −78.6 to−85.2 (26F), −129.5 (4F), −131.6 (2F), −145.1 (2F).

Example 2-2 Example for Production of CF₃CF[OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃] CF₂OCOCF(CF₃)OCF₂CF(CF₃)OCF₂CF₂CF₃ by FluorinationReaction

Into a 500 cc nickel autoclave, R-113 (313 g) was added, stirred andmaintained at 25° C. At the gas outlet of the autoclave, a coolermaintained at 20° C., a layer packed with NaF pellets and a coolermaintained at −10° C., were installed in series. Further, a liquidreturning line to return the condensed liquid from the cooler maintainedat −10° C. to the autoclave, was installed. Nitrogen gas was suppliedfor 1.0 hour and then, fluorine gas diluted to 20% by nitrogen gas, wassupplied at a flow rate of 7.28 L/hr, and the internal pressure of thereactor was maintained at 0.15 MPa. Then, while supplying fluorine gasdiluted to 20% by nitrogen gas, at the same flow rate and whilemaintaining the internal pressure of the reactor at 0.15 MPa, a solutionobtained by dissolving the product (50.3 g) obtained in Example 2-1 inR-113 (250 g), was injected over a period of 8.3 hours.

Then, while supplying fluorine gas diluted to 20% by nitrogen gas at thesame flow rate and while maintaining the pressure of the reactor at 0.15MPa, a R-113 solution having a benzene concentration of 0.01 g/ml, wasinjected in an amount of 9 ml while raising the temperature from 25° C.to 40° C., whereupon the benzene injection inlet of the autoclave wasclosed, and stirring was continued for 0.3 hour. Then, while maintainingthe pressure of the reactor at 0.15 MPa and the internal temperature ofthe reactor at 40° C., the above benzene solution was injected in anamount of 6 ml, and stirring was continued for 0.3 hour. The sameoperation was repeated ten times, and further stirring was continued for0.7 hour. The total amount of benzene injected was 0.76 g, and the totalamount of 1,1,2-trichlorotrifluoroethane injected was 75 ml. Further,nitrogen gas was supplied for 1.0 hour. The formed product wasquantatively analyzed by ¹⁹F-NMR (internal standard: C₆F₆), whereby theyield of the above identified compound was 81%.

¹⁹F-NMR (376.0 MHz, solvent: CDCl₃, standard: CFCl₃)

δ (ppm): −77.6 (2F), −78.5 to −87.6 (29F), −130.1 (4F), −132.1 (2F),−142.2 to −144.5 (1F), −145.2 to −147.1 (2F).

Example 2-3 Example for Production of CF₃COCOF by Liquid Phase Pyrolysis

The formed product obtained in Example 2-2 (42.0 g) was charged into a200 cc autoclave together with KF powder (0.5 g) andCF₃CFHOCF₂CF(CF₃)OCF₂CF₂CF₃ and heated in a sealed state at from 80 to120° C. for 13 hours and 120° C. for 14 hours in an oil bath, whilevigorously stirring. At the outlet of the autoclave, a pressureresistant container cooled to −78° C. was installed, and when theinternal pressure of the reactor became at least 0.28 MPa, the gas inthe reactor was liquefied and recovered. 0.8 g of a sample wasrecovered. The recovered sample was gaseous at room temperature, and asa result of the analysis by GC-MS, the above-identified compound wasconfirmed to be the main product. The yield of the above-identifiedcompound was 9.4%.

INDUSTRIAL APPLICABILITY

As described in the foregoing, by the present invention, a fluorinatedpolyvalent carbonyl compound can be produced by an economicallyadvantageous process from inexpensive materials without requiring acomplicated synthetic step.

The entire disclosure of Japanese Patent Application No. 2000-294801filed on Sep. 27, 2000 including specification, claims and summary isincorporated herein by reference in its entirety.

1. A process for producing a fluorinated polyvalent carbonyl compound(5), which comprises reacting a compound of the following formula (1)with a compound of the following formula (2) to obtain a compound of thefollowing formula (3) having a fluorine content of at least 30 mass %,then reacting the compound of the formula (3) with fluorine in a liquidphase to obtain a compound of the following formula (4) and cleaving theester bonds derived from primary and secondary alcohols in the compoundof the formula (4):

wherein each of R¹, R², R³ and R⁴ which may be the same or different, isa monovalent organic group; Q^(H) is a (m+n+p)valent organic group or asingle bond; R^(1F), R^(2F), R^(3F), R^(4F) and Q^(F) are the samegroups as R¹, R², R³, R⁴ and Q^(H), respectively, or groups having R¹,R², R³, R⁴ and Q^(H) fluorinated, respectively; X is a halogen atom;otherwise, R² and R³, or R^(2F) and R^(3F), may, respectively, beconnected to constitute a bivalent group; each of m, n and p is aninteger of at least 0, provided that (m+n+p)≧2 and n and p are not 0 atthe same time, and when m is 1, n is 1, and p is 0, or when m is 1, n is0, and p is 1, Q^(H) may be a single bond, and when Q^(H) is a singlebond, Q^(F) is a single bond.
 2. The process according to claim 1,wherein a compound of the following formula (6) is obtained, togetherwith the compound of the formula (5), from the reaction product obtainedby cleaving the ester bonds derived from the primary and secondaryalcohols in the compound of the formula (4):

wherein R^(4F) is as defined above.
 3. The process according to claim 1,wherein m is an integer of at least 1, n is an integer of at least 0,and p is an integer of at least 1, or m is an integer of at least 1, nis an integer of at least 1, and p is an integer of at least
 0. 4. Theprocess according to claim 1, wherein Q^(H) is a (m+n+p)valent saturatedorganic group having hydrogen atoms, and Q^(F) is a (m+n+p)valentperfluorinated saturated organic group having all hydrogen atoms inQ^(H) substituted by fluorine atoms.
 5. The process according to claim1, wherein each of R¹, R² and R³ which may be the same or different, isa monovalent saturated organic group having hydrogen atoms, and each ofR^(1F), R^(2F) and R^(3F) is a monovalent perfluorinated saturatedorganic group having all hydrogen atoms in the saturated organic groupsubstituted by fluorine atoms.
 6. The process according to claim 1,wherein R⁴ and R^(4F) are monovalent perfluorinated saturated organicgroups having the same structure.
 7. The process according to claim 2,wherein the compound of the formula (2) has the same structure as thecompound of the formula (6), and at least a part of the compound of theformula (6) obtained from the reaction product obtained by cleaving theester bonds in the compound of the formula (4) is used as at least apart of the compound of the formula (2) to be reacted with the compoundof the formula (1), so that the compound of the formula (5) can beobtained continuously.
 8. The process according to claim 1, wherein thefluorine content of the compound (3) ranges from 30 to 86 mass %.
 9. Theprocess according to claim 1, wherein the fluorine content of thecompound (3) ranges from 30 to 76 mass %.
 10. The process according toclaim 1, wherein the fluorine is present in an amount that is at least1.5 mole equivalent with respect to the compound (3).
 11. The processaccording to claim 10, wherein the cleaving comprises heating compound(4).
 12. The process according to claim 10, wherein the cleavingcomprises contacting the compound (4) with a solid nucleophilic agent inthe absence of a solvent.
 13. The process according to claim 1, whereinthe cleaving comprises heating compound (4) at a temperature.
 14. Theprocess according to claim 13, wherein the temperature ranges from 50°C. to 350° C.
 15. The process according to claim 13, wherein thetemperature ranges from 50° C. to 300° C.
 16. The process according toclaim 13, wherein the temperature ranges from 150° C. to 250° C.
 17. Theprocess according to claim 1, wherein the cleaving comprises contactingthe compound (4) with a solid nucleophilic agent in the absence of asolvent.
 18. The process according to claim 17, wherein the solidnucleophilic agent comprises a salt selected from the group consistingof NaF, NaHF₂, KF, CsF, and combinations thereof.
 19. The processaccording to claim 17, wherein the solid nucleophilic agent comprises asalt selected from the group consisting of NaF, NaHF₂, and combinationsthereof.
 20. The process according to claim 17, wherein the solidnucleophilic agent comprises NaF.
 21. The process according to claim 2,wherein the compound (1) is the following compound (10), the compound(2) is the following compound (11), the compound (3) is the followingcompound (7), the compound (4) is the following compound (8), thecompound (5) is the following compound (9), and the compound (6) is thefollowing compound (12):


22. The process according to claim 21, which further comprises reactingcompound (9) with hexafluoropropylene oxide to obtain a product;pyrolyzing the product to obtain a pyrolyzed product with the followingformula (13)F₂C═CFO(CF₂)₂C(CF₃)₂OCOCF₂CF₃  (13).
 23. The process according to claim22, which further comprises hydrolyzing the pyrolyzed product with theformula (13) to obtain a hydrolyzed product with the following formula(14)F₂C═CFO(CF₂)₂C(CF₃)₂OH  (14).
 24. The process according to claim 23,which further comprises polymerizing the hydrolyzed product with theformula (14) to obtain a polymer.